CN103641785A - Ionic liquid and preparation method thereof - Google Patents
Ionic liquid and preparation method thereof Download PDFInfo
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- CN103641785A CN103641785A CN201310573537.2A CN201310573537A CN103641785A CN 103641785 A CN103641785 A CN 103641785A CN 201310573537 A CN201310573537 A CN 201310573537A CN 103641785 A CN103641785 A CN 103641785A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D233/00—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings
- C07D233/54—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members
- C07D233/56—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms
- C07D233/58—Heterocyclic compounds containing 1,3-diazole or hydrogenated 1,3-diazole rings, not condensed with other rings having two double bonds between ring members or between ring members and non-ring members with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring carbon atoms with only hydrogen atoms or radicals containing only hydrogen and carbon atoms, attached to ring nitrogen atoms
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01D11/04—Solvent extraction of solutions which are liquid
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Abstract
The invention discloses a method for synthesizing a novel trinuclear ionic liquid. The method comprises the following steps: taking 4-methyl acetophenone as a raw material and adding a catalyst to prepare 1, 3, 5-tri(4-methylphenyl) phene; performing bromination to obtain 1, 3, 5-tri(bromobenzyl) phene; and introducing alkyl imidazole and performing anion replacement to prepare the novel trinuclear ionic liquid. The method for synthesizing the trinuclear ionic liquid is simple, operation is simple, solvent consumption is small and yield is relatively high.
Description
Technical field
The present invention relates to ionic liquid field, be specifically related to a kind of ionic liquid and preparation method thereof.
Background technology
Ionic liquid (Ionic Liquid) refers to completely the salt that is formed, is in a liquid state under low temperature (<100 ℃) by ion, also referred to as room temperature melting salt (room temperature molten salts), organic ion liquid etc., go back without unified title at present, but tend to be called for short ionic liquid.Organic cation and inorganic anion that it is generally equated by number form, on the whole aobvious electric neutrality; Be all generally liquid at normal temperatures, thereby ionic liquid often show unique character and distinctive function.
As the green solvent of the novel replacement volatile organic solvent of a class, ionic liquid has the distinguishing feature that conventional solvent does not have, and can reduce and even eliminate solvent pollution on the environment.Ionic liquid has: (1) ionic liquid has wider liquid temperature scope.(2) ion liquid dissolving ability is strong.(3) ionic liquid steam forces down, not volatile.(4) stability is high.(5) features such as large (6) electroconductibility of viscosity of il is good.In the prior art, synthetic ionic liquid mainly be take monokaryon and a small amount of double-core as main.But existing ionic liquid kind is few, can't meet actual needs.
Summary of the invention
The object of this invention is to provide a kind of ionic liquid, compared with other ionic liquid, structurally had the feature of three cores, at complexometric extraction, the aspects such as catalysis have good application prospect.
The present invention also provides the preparation method of above-mentioned ionic liquid, and this preparation method is consuming time few, and save energy is simple to operate, and solvent-oil ratio is little, and productive rate is higher.
Object of the present invention adopts following technical scheme to realize.
An ionic liquid, its structural formula is suc as formula shown in I:
X wherein
-for BF
4 -or PF
6 -.
A method of preparing described ionic liquid, comprises the steps:
(1) 1, between 3,5-, three (to methyl) phenyl benzene generation bromine substitution reaction, obtains three (bromobenzyl) benzene between 1,3,5-;
(2) 1, between 3,5-, three (bromobenzyl) benzene reacts with Methylimidazole, obtains bromo three core ionic liquids;
(3) bromo three core ionic liquids and Potassium Hexafluorophosphate or sodium tetrafluoroborate generation negatively charged ion replacement(metathesis)reaction obtain described novel three core ionic liquids.
Concrete grammar in step (1) is: in solvent, between 1,3,5-, three (to methyl) phenyl benzene and N-bromo-succinimide, under the effect of Diisopropyl azodicarboxylate, bromine substitution reaction occurs; After reaction finishes, cross leaching filtrate, except desolventizing obtains three (bromobenzyl) benzene between 1,3,5-.
In step (1), between N-bromo-succinimide and 1,3,5-, the mol ratio of three (to methyl) phenyl benzene is 3-10:1, and between Diisopropyl azodicarboxylate and 1,3,5-, the mass ratio of three (to methyl) phenyl benzene is 0.05-0.15:1.
In step (1), the condition of bromine substitution reaction is: under whipped state, reaction system is heated to 50 ℃ of-80 ℃ of backflows, reaction 1-5h.
The concrete grammar of step (2) is: between 1,3,5-, three (bromobenzyl) benzene is dissolved in solvent, under nitrogen protection, drips Methylimidazole, is heated to 60-150 ℃ of backflow under whipped state, reaction 18-30h; After reaction finishes, water extraction, except anhydrating, obtains bromo three core ionic liquids; The add-on of described Methylimidazole is 3-10 times of three (bromobenzyl) benzene amount of substance between 1,3,5-.
The concrete grammar of step (3) is: in solvent, bromo three core ionic liquid are reacted under whipped state with Potassium Hexafluorophosphate or sodium tetrafluoroborate, and after reaction finishes, the solid product obtaining after suction filtration is described novel three core ionic liquids.
In step (3), the reaction times while using Potassium Hexafluorophosphate is 20-30h; Reaction times while using sodium tetrafluoroborate is 2-4 days.
The solvent that reaction system is used is tetracol phenixin, acetone, DMF, THF or methyl alcohol.
Between 1,3,5-, the preparation method of three (to methyl) phenyl benzene is: 4-methyl acetophenone is dissolved in to dehydrated alcohol, under whipped state, slowly adds SiCl
4react, after reaction finishes, reaction mixture is poured into water, with dichloromethane extraction, dry, after concentrating, use dehydrated alcohol crystallization, obtain three (to methyl) phenyl benzene between 1,3,5-.
The ionic liquid providing of the present invention, compares with other ionic liquid, structurally has the feature of three cores, at aspects such as complexometric extractions, has good application prospect.
The present invention also provides the preparation method of above-mentioned ionic liquid, and this preparation method is consuming time few, and save energy is simple to operate, and solvent-oil ratio is little, and productive rate is higher.
Accompanying drawing explanation
Fig. 1 represents to prepare the reaction process of three (to methyl) phenyl benzene between 1,3,5-, and wherein II is 4-methyl acetophenone, and III is three (to methyl) phenyl benzene between 1,3,5-.
Fig. 2 represents to prepare the reaction process of three (bromobenzyl) benzene between 1,3,5-, and wherein III is three (to methyl) phenyl benzene between 1,3,5-, and IV is three (bromobenzyl) benzene between 1,3,5-.
Fig. 3 prepares the reaction process of bromo three core ionic liquid, and IV is three (bromobenzyl) benzene between 1,3,5-, and V is bromo three core ionic liquid.
Fig. 4 prepares the reaction process of novel ion liquid, and V is bromo three core ionic liquid, and VI is the novel three core ionic liquids of the present invention.
Embodiment
Embodiment 1
(1) prepare three (to methyl) phenyl benzene between 1,3,5-
On the basis of document, improve three (to methyl) phenyl benzene between preparation 1,3,5-.（Saad?S.Elmorsy,Andrew?Pelter?and?Keith?Smith,The?Direct?Production?of?Tri-and?Hexa-Substituted?Benzenes?form?Ketones?under?Mild?Conditions.Tclrahcdron?L.&m,Vol32,No33,pp41754176.19，1991）
Under room temperature, in the there-necked flask of 100ml, add the 4-methyl acetophenone of 0.01mol, and then add the dehydrated alcohol of 20ml, under whipped state, with feeder, slowly add 0.01mol(1.7g, 1.2ml) SiCl
4, after reaction 6h, finish reaction.Reaction mixture is poured in the water of 40ml, with twice of the dichloromethane extraction of 35ml, combined dichloromethane, add anhydrous magnesium sulfate drying three hours, filter afterwards and remove siccative, then filtrate rotary evaporation is concentrated, add a small amount of dehydrated alcohol, be put in crystallization in refrigerator, finally filter and obtain solid product.Reaction process as shown in Figure 1.
(2) prepare three (bromobenzyl) benzene between 1,3,5-
In the there-necked flask of 100ml, add reactant 1,3, three (to methyl) phenyl benzene 0.01mol between 5-, then add CCl
430ml, as solvent, adds initiator Diisopropyl azodicarboxylate (AIBN), finally adds N-bromo-succinimide (NBS) 0.06mol again, under whipped state, is heated to 76 ℃ of back flow reaction 1 hour.After reaction finishes, standing cooling, remove by filter insoluble succimide, filtrate rotary evaporation, except desolventizing, is obtained to i.e. three (bromobenzyl) benzene between 1,3,5-of solid product.The add-on of initiator Diisopropyl azodicarboxylate (AIBN) be between 1,3,5-three (to methyl) phenyl benzene quality 10%.Reaction process as shown in Figure 2.
(3) prepare bromo three core ionic liquids
The reaction substrate 1,3 that adds 0.01mol in there-necked flask, between 5-, three (bromobenzyl) benzene, adds CCl
430ml, as solvent, the in the situation that of nitrogen protection, drips Methylimidazole 0.06mol in bottle, is heated to 80 ℃ of backflows under whipped state, reaction 24h.Reaction finishes rear standing, adds distilled water in bottle, extraction product twice, then remove distilled water, obtain bromo three core ionic liquids.Reaction process as shown in Figure 3.
(4) prepare novel three core ionic liquids
Under 25 degree conditions, bromo three core ionic liquid 0.01mol are joined in 40ml methyl alcohol, add 0.06mol Potassium Hexafluorophosphate, under agitation condition, react 24h, finish after reaction, suction filtration is removed solvent and unnecessary Potassium Hexafluorophosphate, the solid product obtaining.
Described solid product is carried out to structural characterization, and result is as follows:
1H?NMR(CDCl
3):δ:3.75(s,9H),5.45(s,6H),7.10-7.89(24H,m);MS-EI(m/z):1024
The explanation of said structure characterization result, solid product is 1 '-[three (bromobenzyl) phenyl between 1,3,5-]-3 ', and 3 ', 3-tri-methylimidazolium phosphofluoric acid, is ionic liquid of the present invention, and its yield is 85%.Reaction process as shown in Figure 4.
Embodiment 2
(1) prepare three (to methyl) phenyl benzene between 1,3,5-, with embodiment 1.
(2) prepare three (bromobenzyl) benzene between 1,3,5-
In the there-necked flask of 100ml, add reactant 1,3, three (to methyl) phenyl benzene 0.01mol between 5-, add again acetone 30ml as solvent, add initiator Diisopropyl azodicarboxylate (AIBN), finally add again N-bromo-succinimide (NBS) 0.1mol, under agitation react, be heated to 50 degree and reflux, react 5 hours.After reaction finishes, standing cooling, remove by filter insoluble succimide, filtrate rotary evaporation, except desolventizing, is obtained to i.e. three (bromobenzyl) benzene between 1,3,5-of solid product.The add-on of initiator Diisopropyl azodicarboxylate (AIBN) be between 1,3,5-three (to methyl) phenyl benzene quality 5%.
(3) prepare bromo three core ionic liquids
The reaction substrate 1,3 that adds 0.01mol in there-necked flask, between 5-, three (bromobenzyl) benzene, adds DMF30ml as solvent, the in the situation that of nitrogen protection, drips Methylimidazole 0.1mol in bottle, is heated to 120 ℃ of back flow reaction 30h under whipped state.Reaction finishes rear standing, adds distilled water in bottle, extraction product twice, then remove distilled water, obtain bromo three core ionic liquids.
(4) prepare novel three core ionic liquids
Under 21 degree conditions, bromo three core ionic liquid 0.01mol are joined to 40mlTHF(solvent) in, add 0.1mol sodium tetrafluoroborate, under agitation condition, react 3 days, finish after reaction, filter and remove solvent and unnecessary sodium tetrafluoroborate, solid matter.
Described solid product is carried out to structural characterization, and result is as follows:
1H?NMR(CDCl
3):δ:3.75(s,9H),5.45(s,6H),7.10-7.89(24H,m);MS-EI(m/z):850。
The explanation of said structure characterization result, solid product is 1 '-[three (bromobenzyl) phenyl between 1,3,5-]-3 ', 3 ', 3-tri-methylimidazolium Tetrafluoroboric acid, is ionic liquid of the present invention, product yield 80%.
Embodiment 3
(1) prepare three (to methyl) phenyl benzene between 1,3,5-, with embodiment 1.
(2) prepare three (bromobenzyl) benzene between 1,3,5-
In the there-necked flask of 100ml, add reactant 1,3, three (to methyl) phenyl benzene 0.01mol between 5-, add again methyl alcohol 30ml as solvent, add initiator Diisopropyl azodicarboxylate (AIBN), finally add again N-bromo-succinimide (NBS) 0.03mol, under agitation react, be heated to 65 degree and reflux, react 3 hours.After reaction finishes, standing cooling, remove by filter insoluble succimide, filtrate rotary evaporation, except desolventizing, is obtained to i.e. three (bromobenzyl) benzene between 1,3,5-of solid product.The add-on of initiator Diisopropyl azodicarboxylate (AIBN) be between 1,3,5-three (to methyl) phenyl benzene quality 15%.
(3) prepare bromo three core ionic liquids
The reaction substrate 1,3 that adds 0.01mol in there-necked flask, between 5-, three (bromobenzyl) benzene, adds methyl alcohol 30ml as solvent, the in the situation that of nitrogen protection, drips Methylimidazole 0.03mol in bottle, is heated to 150 ℃ of backflows under whipped state, reaction 18h.Reaction finishes rear standing, adds distilled water in bottle, extraction product twice, then remove distilled water, obtain bromo three core ionic liquids.
(4) prepare novel three core ionic liquids
Under 18 ℃ of conditions, bromo three core ionic liquid 0.01mol are joined to 40mlCCl(solvent) in, add 0.03mol sodium tetrafluoroborate, under agitation condition, react 4 days, finish after reaction, filter and remove solvent and unnecessary sodium tetrafluoroborate, solid matter.
Described solid product is carried out to structural characterization, and result is as follows:
1H?NMR(CDCl
3):δ:3.75(s,9H),5.45(s,6H),7.10-7.89(24H,m);MS-EI(m/z):850
The explanation of said structure characterization result, solid product is 1 '-[three (bromobenzyl) phenyl between 1,3,5-]-3 ', 3 ', 3-tri-methylimidazolium a tetrafluoro borate,, be ionic liquid of the present invention, product yield 84%.
Embodiment 4
Extraction of Heavy Metals example
(1), get Pb
2+ionic concn is the simulated wastewater solution 10mL of 30mg/L and the ionic liquid of 2mL embodiment 1 preparation, puts into tool lid Erlenmeyer flask, and mixing shakes up, under normal temperature (25 ℃) condition, and constant temperature oscillation 30min.
(2), centrifugation, get upper strata water and survey its absorbancy with atomic absorption spectrophotometer, according to typical curve, obtain Pb in water
2+concentration value and calculate Pb
2+percentage extraction.Found that, the ionic liquid of embodiment 1 preparation is to Pb
2+percentage extraction is 80%.
According to the method described above, adopt the novel three core ionic liquids of the embodiment of the present invention 1,2,3 preparations respectively to containing Pb
2+, Cu
2+, Cd
2+and Zn
2+the research that the extraction ability of four heavy metal species ions carries out, finds that novel three core ionic liquids extraction ability under the same conditions prepared by the present invention is all better than [AMIM] [PF
6] (1-allyl group-3-Methylimidazole phosphofluoric acid).
Claims (10)
1. an ionic liquid, its structural formula suc as formula
shown in:
X wherein
-for BF
4 -or PF
6 -.
2. a method of preparing ionic liquid described in claim 1, is characterized in that comprising the steps:
(1) 1, between 3,5-, three (to methyl) phenyl benzene generation bromine substitution reaction, obtains three (bromobenzyl) benzene between 1,3,5-;
(2) 1, between 3,5-, three (bromobenzyl) benzene reacts with Methylimidazole, obtains bromo three core ionic liquids;
(3) bromo three core ionic liquids and Potassium Hexafluorophosphate or sodium tetrafluoroborate generation negatively charged ion replacement(metathesis)reaction obtain described ionic liquid.
3. method according to claim 2, is characterized in that the concrete grammar in step (1) is: in solvent, between 1,3,5-, three (to methyl) phenyl benzene and N-bromo-succinimide, under the effect of Diisopropyl azodicarboxylate, bromine substitution reaction occurs; After reaction finishes, cross leaching filtrate, except desolventizing obtains three (bromobenzyl) benzene between 1,3,5-.
4. method according to claim 3, is characterized in that N-bromo-succinimide and 1,3 in step (1), between 5-, the mol ratio of three (to methyl) phenyl benzene is 3-10:1, between Diisopropyl azodicarboxylate and 1,3,5-, the mass ratio of three (to methyl) phenyl benzene is 0.05-0.15:1.
5. method according to claim 4, is characterized in that: in step (1), the condition of bromine substitution reaction is: under whipped state, reaction system is heated to 50 ℃--80 ℃ of backflows, reaction 1-5h.
6. method according to claim 4, is characterized in that the concrete grammar of step (2) is: between 1,3,5-, three (bromobenzyl) benzene is dissolved in solvent, under nitrogen protection, drips Methylimidazole, is heated to 60-150 ℃ of backflow under whipped state, reaction 18-30h; After reaction finishes, water extraction, except anhydrating, obtains bromo three core ionic liquids; The add-on of described Methylimidazole is 3-10 times of three (bromobenzyl) benzene amount of substance between 1,3,5-.
7. method according to claim 6, the concrete grammar that it is characterized in that step (3) is: in solvent, bromo three core ionic liquid are reacted under whipped state with Potassium Hexafluorophosphate or sodium tetrafluoroborate, and after reaction finishes, the solid product obtaining after suction filtration is described novel three core ionic liquids.
8. method according to claim 7, is characterized in that: in step (3), the reaction times while using Potassium Hexafluorophosphate is 20-30h; Reaction times while using sodium tetrafluoroborate is 2-4 days.
9. according to the described method of one of claim 2-8, it is characterized in that: the solvent that reaction system is used is tetracol phenixin, acetone, DMF, THF or methyl alcohol.
10. method according to claim 9, is characterized in that: between 1,3,5-, the preparation method of three (to methyl) phenyl benzene is: 4-methyl acetophenone is dissolved in to dehydrated alcohol, under whipped state, slowly adds SiCl
4react, after reaction finishes, reaction mixture is poured into water, with dichloromethane extraction, dry, after concentrating, use dehydrated alcohol crystallization, obtain three (to methyl) phenyl benzene between 1,3,5-.
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| CN2012104776099A CN102977030A (en) | 2012-11-22 | 2012-11-22 | Novel trinuclear ionic liquid and preparation method thereof |
| CN201210477609.9 | 2012-11-22 | ||
| CN201310573537.2A CN103641785B (en) | 2012-11-22 | 2013-11-15 | Ionic liquid and preparation method thereof |
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| CN201310573537.2A Expired - Fee Related CN103641785B (en) | 2012-11-22 | 2013-11-15 | Ionic liquid and preparation method thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732695A (en) * | 2016-04-29 | 2016-07-06 | 南京信息工程大学 | Tree-shaped framework ion liquid as well as preparation method and application of tree-shaped framework ion liquid |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006012513A2 (en) * | 2004-07-23 | 2006-02-02 | Sigma-Aldrich Co. | High stability diionic liquid salts |
| WO2008005906A2 (en) * | 2006-07-03 | 2008-01-10 | Matheson Tri-Gas, Inc. | Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation |
| US20100154889A1 (en) * | 2008-12-19 | 2010-06-24 | Industrial Technology Research Institute | Electrolyte composition and dye-sensitized solar cell using the same |
-
2012
- 2012-11-22 CN CN2012104776099A patent/CN102977030A/en active Pending
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2013
- 2013-11-15 CN CN201310573537.2A patent/CN103641785B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2006012513A2 (en) * | 2004-07-23 | 2006-02-02 | Sigma-Aldrich Co. | High stability diionic liquid salts |
| WO2008005906A2 (en) * | 2006-07-03 | 2008-01-10 | Matheson Tri-Gas, Inc. | Fluid storage and purification method and system using ionic liquid in particular di-imidazolium cation |
| US20100154889A1 (en) * | 2008-12-19 | 2010-06-24 | Industrial Technology Research Institute | Electrolyte composition and dye-sensitized solar cell using the same |
Non-Patent Citations (2)
| Title |
|---|
| 王仲妮等: "咪唑类离子液体的研究进展", 《化学进展》 * |
| 赵地顺等: "双核离子液体的合成及其对酯化反应的催化活性", 《有机化学》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105732695A (en) * | 2016-04-29 | 2016-07-06 | 南京信息工程大学 | Tree-shaped framework ion liquid as well as preparation method and application of tree-shaped framework ion liquid |
| CN105732695B (en) * | 2016-04-29 | 2018-06-12 | 南京信息工程大学 | A kind of tree-shaped skeleton ionic liquid and preparation method and application |
Also Published As
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| CN102977030A (en) | 2013-03-20 |
| CN103641785B (en) | 2015-03-25 |
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